BR112020021041A2 - FIRE SUPPRESSOR FOAM FORMING COMPOSITIONS, PRECURSORS, THEIR USES AND METHODS OF PREPARING THEM - Google Patents

Abstract

the present invention relates to aqueous fire suppression compositions, comprising surfactants and / or hydrotropes, particulate inorganic materials selected from the group consisting of perlite, talc, calcium carbonate, kaolin, dolomite, mica and bentonite, and their combinations, and optionally one or more additives. the invention also relates to the uses of such particulate inorganic materials, as well as to dry precursor compositions, fire suppression compositions and methods of preparing them.

Description

Invention Patent Descriptive Report for "FIRE-SUPPRESSING FOAM-FORMING COMPOSITIONS, PRECURSORS, THEIR USES AND PREPARATION METHODS".

FIELD OF THE INVENTION

[0001] The present invention relates to both water and dry compositions to form suitable foams as fire-extinguishing compositions and to fire-extinguishing foams. The invention also relates to the use of particulate inorganic materials in the formation of foams, methods for improving foam stability and methods for improving the fire-extinguishing properties of foams.

BACKGROUND OF THE INVENTION

[0002] Aqueous foams are used to attack so-called class B fires (liquid fuel). Foams are particularly used outdoors when dealing with large-scale fires and fire hazards. Examples of use are for fire suppression and prevention in aircraft and marine vessels, civil aviation facilities, such as airports, and in industrial facilities where large volumes of potentially flammable liquids are used or stored, for example , petrochemical refineries, equipment and oil and gas platforms. The other means of extinguishing fire, applied in drums, are more commonly employed against small scale class B fire hazards.

[0003] According to the state of the art, the type of foam preferred for this application, based on performance, are the so-called aqueous film-forming foams (AFFF). Major foam users often specify only the use of this type of foam, which takes advantage of its unique ability to spread through liquid fuel (oil). This property is linked to the very low aqueous surface stresses of its solutions. Since the foam provides a blanket covering over the fuel, it must withstand the fuel's tendency to destabilize the foam and must also prevent flammable vapor from the fuel from passing through the foam layer and contacting the fuel. air above it and thus ignite. In the state of the art, this film-forming effect is conferred by fluorocarbon (FC) surfactants, as, for example, shown in US 4,424,133 A.

[0004] However, in recent years, CF surfactants have been analyzed, as they tend to persist in the environment and can be toxic to aquatic life. Cs chain-length FC surfactants are particularly harmful and are now being banned by the competent authorities or subject to a self-imposed industry ban. By reducing the chain length from Cs to Cs, they are less harmful, but there is still concern and it is likely that, later on, the use of all CF surfactants in this application will be prohibited.

[0005] Recognizing this, fire-fighting foam producers are looking for alternative formulations based on a non-CF surfactant. Some already exist and are used, although none have the AFFFs' filmmaking capabilities. An improvement that is being sought and that can be realistically expected with the newly developed formulations is a longer foam life, that is, an improved foam stability. In non-FC based formulations being developed, as, for example, disclosed in WO 2012/123778 A1, attempts are being made to improve foam stability by using new surfactants and polymers (gums). However, the problem is that such gums often act to increase viscosity and lead to problems with the shelf life, since mixtures of components tend to separate. The high viscosity and separation of the components lead to problems when the compositions are diluted and / or foamed before use, although it is essential that the compositions are easy to use and reliable.

[0006] For example, US 2016/0023032 A1 discloses fire-fighting compositions that comprise a combination of a high molecular weight water-soluble anionic acrylic polymer, a polysaccharide gum and a surfactant, and which can achieve extinguishing properties fire rates, while having acceptable viscosity and storage stability. However, these fire-fighting compositions are limited to very specific high molecular weight polymers in combination with specific gums.

[0007] WO 2017/161162 A1 discloses fluorine-free fire-extinguishing foams that comprise new organosiloxane compounds that are intended to improve the spread and film formation of foams. Although the new organosiloxane compounds may be easier to synthesize than the previous compounds containing organosilicon, these compounds are not currently available on the market and separate production and distribution channels are required.

[0008] US 2017/0368395 A1 discloses fluorine-free fire extinguishing foams that comprise a combination of two different surfactants, used in specific weight ratios. The foams disclosed there achieve good coefficients of propagation and fire extinguishing in small scale aviation fuel fires. However, without the use of foam stabilizers, foam stability is expected to be low.

[0009] The prior art, therefore, poses several different problems.

BRIEF DESCRIPTION OF THE INVENTION

[00010] The present invention is defined in the appended claims.

[00011] In particular, the present invention is accomplished by an aqueous fire suppression composition, the composition comprising a surfactant and / or a hydrotrope and a particulate inorganic material, selected from the group consisting of perlite, talc , calcium carbonate, kaolin, dolomite, mica and bentonite, and their combinations. According to certain embodiments, the aqueous composition according to the present invention can further comprise one or more additives. In accordance with the present invention, aqueous foam-forming compositions are provided which do not require the use of fluorinated compounds and which have good fire-fighting properties, in particular for class B fires.

[00012] In a certain modality, the surfactant comprised in the aqueous composition of the present invention can be selected from the group of cationic surfactants, non-ionic surfactants and anionic surfactants. For example, the surfactant can be a cationic surfactant, such as, for example, an alkyl trimethyl ammonium halide, such as tetradecyl trimethyl ammonium bromide or dichododimethylammonium chloride, or dihydrogenated sebum-oilethyl methoxide. or a polymeric quaternary ammonium ester. According to a separate modality, the surfactant can be an anionic surfactant selected from alkyl ether sulfates, such as sodium lauryl ether sulfate, and alkyl sulfates, such as sodium lauryl sulfate. These types of surfactants have been found to be particularly useful in the present invention.

[00013] In a certain modality, the particulate inorganic material can be selected from the group consisting of talc, carbon

calcium, mica and kaolin. In another embodiment, the particulate inorganic material may be talc, such as, for example, microcrystalline talc, macrocrystalline talc or a mixture thereof. These particulate inorganic materials have been found to offer particularly good performance. In a separate embodiment, the particulate inorganic material can be synthetic talc.

[00014] “According to another modality, microcrystalline talc can have a dso of 10 µm or less, such as 5 µm or less, such as ranging from 0.01 to 3.0 µm, such as about 0.01 µm or about 1.0 µm or about 2.0 µm. Depending on the intended use of the aqueous composition according to the present invention, various particle size distributions can be selected.

[00015] In a certain modality, the ratio of surfactant to water is in the range of 0.01 to 5% by weight. It was found that, within this range, the best results were obtained in relation to fire extinguishing properties, storage properties, as well as environmental sustainability.

[00016] In a certain modality, the ratio of particulate inorganic powder to surfactant is in the range of 500: 1 to 1: 1. In accordance with the present invention, the aqueous composition can be provided as a ready-to-use composition, or as a concentrate, which, at the time of use in the fire extinguishing application, requires dilution using readily available local water sources. , including sources of salt water, sea water and fresh water.

[00017] Also part of the present invention are dry precursor compositions comprising a surfactant and / or a hydrotrope, and a particulate inorganic material, selected from the group consisting of perlite, talc, calcium carbonate, dolomite , mica and bentonite, and their combinations, and, optionally, one or more additives. Such precursor compositions were found to be, on the one hand, easy to handle and store, while, on the other hand, after adding water to obtain an aqueous composition according to the present invention, they gave foams particularly stable and durable for use in fire extinguishing applications.

[00018] According to one embodiment, the dry precursor composition according to this invention has a weight ratio of particulate inorganic powder to surfactant in the range of 500: 1 to 1: 1.

[00019] According to a separate embodiment, the invention relates to a fire-extinguishing foam comprising the aqueous composition according to the present invention. For example, the aqueous composition according to the invention can be made into foam using means known to the person skilled in the art to obtain the fire extinguishing foam according to the invention.

[00020] Methods of preparing fire-extinguishing foams using dry precursor compositions and / or aqueous compositions according to the present invention are also part of the present invention. According to a particular modality, the method comprises the steps of providing a mixture of water and surfactant and / or a hydrotrope, providing a particulate inorganic material, selected from the group consisting of perlite, talc, carbonate of calcium, dolomite, mica and bentonite and their combinations, optionally providing one or more additives, mixing the mixture of water and surfactant and / or a hydrotrope, the particulate inorganic material provided and optionally said one or more additives provided and finally, transform the obtained mixture into foam. It has been found that good foam stability can be achieved using the forming method according to the present invention.

[00021] According to a separate modality, the method comprises the steps of providing a dry precursor of the present invention, providing water, optionally providing one or more additives, mixing the dry precursor provided, the water provided and optionally the one or more additives provided and, finally, transform the obtained mixture into foam. It has been found that good foam stability can be achieved using the forming method according to the present invention.

[00022] “Also part of the present invention is the use of particulate inorganic materials in an aqueous composition according to the invention and, by extension, in a fire extinguishing foam according to the present invention. According to this invention, the particulate inorganic materials for said use are selected from the group consisting of perlite, talc, calcium carbonate, dolomite, mica and bentonite, and their combinations.

[00023] Also part of the present invention is a fire extinguishing method which comprises the use of a particulate inorganic mineral according to the present invention or an aqueous composition according to the present invention.

BRIEF DESCRIPTION OF THE FIGURES

[00024] The invention will be further illustrated by reference to the following figure: Fig. 1 graphically shows Examples 10 to 39 of the experimental section disclosed in this document (see below), as well as the geographical origin of the various talc samples tested .

[00025] It is understood that the description and references to the figures that follow refer to illustrative modalities of the present invention and should not limit the scope of the claims.

DETAILED DESCRIPTION OF THE INVENTION

[00026] The present invention, according to the previous claims

provides an aqueous composition for foaming, in particular a foam for use in fire extinguishing applications, in particular for class B fires. Aqueous foams are already used to extinguish fires. class B. The foams according to the present invention avoid the need to use FC-based formulations and are environmentally friendly, at the same time they use readily available components and improve the fire-extinguishing properties by increasing the foam stability.

[00027] In accordance with the present invention, it has been found that more stable foams can be formed by the addition of particulate inorganic materials to aqueous foam-forming compositions. In particular, it has been found that foams formed in accordance with the present invention do not collapse as easily as foams in the prior art and retain their foam structure for a longer period. While in laboratory tests, it was found that the foams of the state of the art lost about 80% or more of their initial mass through water drainage, within 10 minutes of formation, it was found that the foams formed according to the present invention they maintained up to 90% of their initial mass after 60 minutes. These values were obtained using the method as described in the Examples section of the present description.

[00028] Without intending to be bound by theory, it is believed that particulate inorganic materials remain at the water-air interface of foam bubbles to improve foam stability. The ratio of surfactant to particulate inorganic material, therefore, needs to be balanced. When there is a lot of surfactant, it absorbs excessively over the inorganic particulate material and causes it to move into the aqueous phase, away from the interface. In a particular mode, the surfactant is above the critical concentration of

cells for good foaming.

[00029] According to the present invention, the surfactants absorb on the inorganic particulate materials in the aqueous composition. These surfactants are also known as collectors. For example, a cationic surfactant can adhere to a negatively charged surface of an inorganic particle, such as talc.

[00030] According to the present invention, an aqueous composition is provided to form a fire-extinguishing foam, the composition comprising a surfactant and / or a hydrotrope, a particulate inorganic material selected from the group consisting of perlite , talc, calcium carbonate, dolomite, mica and bentonite, and combinations thereof, and, optionally, one or more additives. Surfactants or hydrotropes

[00031] Surfactants or foaming agents, for example, for use in foams for fire extinguishing applications, are known in the art. In certain embodiments, the surfactant comprises either one or more anionic surfactants, or one or more cationic surfactants, or one or more non-ionic surfactants, or combinations thereof.

[00032] Suitable anionic surfactants include, but are not limited to, alkyl ether sulfates, such as sodium lauryl ether sulfate, and alkyl sulfates, such as sodium lauryl sulfate. Suitable anionic surfactants also include ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine laureth sulfate, monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate, lauric monoglyceride sodium sulphate, sodium lauryl sulphate, sodium laureth sulphate, potassium laureth sulphate, sarcosinate lauryl sulphate sodium, sodium lauroyl sarcosinate, potassium lauryl sulfate, sodium trideceth sulfate, sodium methyl lauroyl taurate, sodium lauroyl isethionate, sodium laureth sulfosuccinate, sodium lauryl sulfosuccinate, tridecyl benzene sulfone- sodium dodecyl benzene sulfonate, sodium lauryl anfoacetate, sodium lauryl sulfoacetate, sodium cocoyl isethionate, sodium methyl cocoyl taurate, te phosphate ester based agents, such as alkyl aryl phosphate ether and alkyl phosphate ether, and mixtures thereof. The anionic surfactant can be, for example, an aliphatic sulphonate, such as a C3-C sulfonate> 22 primary alkane, a Cg-C disulfonate> 2 primary alkane, a Ca-C2 sulfonate> alkene, a Cg-C sulfonate> 22 hydroxyalkane or an alkyl glycerol sulfonate ether.

[00033] Suitable cationic surfactants include, but are not limited to, alkyl trimethyl ammonium halides or dialkyl dimethyl ammonium halides, where the alkyl group can comprise 8 to 24 carbon atoms, such as, for example , 10 or 12 or 14 or 16 or 18 or 20 or 22 carbon atoms, such as tetradecyltrimethylammonium bromide or dicocodimethylammonium chloride. The other suitable cationic surfactants are quaternary ammonium species, such as dihydrogenated sebum-oilethyl hydroxyethylammonium methosulfate, or polymeric quaternary ammonium esters, as described in US 8,936,159 B2, the contents of which are incorporated therein. document by reference. Without wishing to be bound by theory, it is believed that a cationic surfactant is likely to act more like a collector acts in flotation systems. Thus, given the negative charge on the surfaces of the particles under conditions of almost neutral pH, it is likely that a cationic surfactant adsorbed more strongly on the particles than an anionic surfactant, which it can still absorb on the talc, but, more likely, for adsorption of its hydrophobic end.

[00034] Suitable non-ionic surfactants include alcohols, acids, amides or alkyl phenols reacted with alkylene oxides, especially ethylene oxide, alone or with propylene oxide. Illustrative non-ionics are the condensates of Ce6-C22 alkyl phenols-ethylene oxide, the condensation products of aliphatic Cs-C13 alcohols, primary or secondary, linear or branched with ethylene oxide and products made by condensation of ethylene oxide reaction products of propylene oxide and ethylene diamine. The other non-ionic ones include long-chain tertiary amine oxides. The other non-ionic ones are co-coamide surfactants and produced by reacting cocoamide with an amine alcohol, such as ethanolamine. Illustrative non-ionics include cocoamide MEA and cocoamide DEA. The other suitable nonionic ones include alkyl polyglycosides, such as decyl glycoside, lauryl glycoside and octyl glycoside.

[00035] In certain embodiments, the surfactant is a sodium lauryl sulfate (or sodium dodecyl sulfate, SDS) or a sodium lauryl ether sulfate (SLES). In certain embodiments, the surfactant is tetradecyltrimethylammonium bromide (TTAB) or dicocodimethylammonium chloride.

[00036] The surfactant must be present in the aqueous composition, according to one aspect of the present invention, in an amount below or above the critical micelle concentration (CMC). CMC is defined as the concentration of surfactants above which the micelles are formed and all additional surfactants added to the system go to the micelles. If there is a lot of surfactant present in the composition, it can move the particulate inorganic material to the aqueous phase, preventing it from exercising its foam stabilizing properties. The ratio of surfactant to inorganic particulate matter, therefore, needs to be balanced. State of the art compositions may require a surfactant to water ratio of up to

5.0% by weight.

[00037] In certain embodiments, the ratio of surfactant to water in the composition according to the invention is in the range of 0.01 to 5% by weight. For example, the ratio of surfactant to water in the composition can be in the range of 0.05 to 4% by weight, such as, for example, 0.1 to 3% by weight, such as, for example, about 0, 05% by weight, about 0.3% by weight, about 0.5% by weight, about 1% by weight, about 2% by weight, about 3% by weight, about 4% by weight or about 5% by weight. For example, according to the present invention, a composition ready to be foamed may have a surfactant to water ratio of about 0.05% by weight to about 0.1% by weight. A concentrate that requires dilution prior to foaming can have a surfactant to water ratio of about 0.5% by weight to about 5% by weight or about 1% by weight. Particulate inorganic material

[00038] “According to the present invention, the stability of the foam formed from the aqueous composition of the invention is improved by the presence of a particulate inorganic material.

[00039] Unless otherwise specified, the particle size properties referred to in this document, for inorganic particulate materials, are as measured in a well-known manner, by sedimenting the particulate material in a fully dispersed condition, in an aqueous medium, using a Sedigraph 5100 machine, as supplied by Micromeritics Instruments Corporation, Norcross, Georgia, USA (website: www.micromeritics.com), referred to in this document as a "Micromeritics Sedigraph 5100 unit". Such a machine provides measurements and a graph of the cumulative percentage by weight of particles having a size, referred to in the art as the 'equivalent spherical diameter' (e.s.d), less than the given e.s.d values. The average particle size dso is the value determined in this mode of the particle's e.s.d in which there is 50% by weight of particles that have an equivalent spherical diameter less than the dso value. The cut-top particle size dao is the value determined in this mode of the particle's e.s.d in which there is 90% by weight of particles that have an equivalent spherical diameter less than the value of dao.

[00040] Particulate inorganic material must have a range of particle sizes that makes it suitable for foam formation, although the range of particle sizes should not be specifically limited. For example, inorganic particulate material can have an average particle size of about 0.01 µm to about 1 mm, provided that stable foams can be formed with such particulate material. For example, the particulate inorganic material may have a dso not greater than about 500 µm, for example, not greater than about 250 µm or not greater than about 100 µm or not greater than about 50 µm. In certain embodiments, the particulate inorganic material has a dso not greater than about 25 µm, for example, not greater than about 10 µm or not greater than about 5 µm or not greater than about 1 µm. In certain embodiments, the inorganic particulate material has a range of about 0.05 µm to about 5 µm, for example, or from about 0.1 µm to about 2.5 µm or from about 0 µm, 5 µm to about 1 µm.

[00041] In certain embodiments, the particulate inorganic material may have a dao not greater than about 1 mm, for example, not greater than about 500 µm or not greater than about 400 µm or not greater than about 300 µm or not greater than about 200 µm or not greater than about 100 µm. In certain embodiments, the inorganic particulate material has a dso not greater than about 50 µm, for example, not greater than about 20 µm or not greater than about 10 µm or not greater than about 5 µm. In certain embodiments, the inorganic particulate material has a dao of about 0.5 µm to about 10 µm, for example, or from about 1 µm to about 7.5 µm or about 2.5 µm at about 5 um.

[00042] In certain modalities, the inorganic particulate material is selected from the group consisting of perlite, talc, calcium carbonate, kaolin, dolomite, mica and bentonite and their combinations.

[00043] In certain modalities, the inorganic particulate material is selected from the group consisting of talc, calcium carbonate, mica, kaolin and their combinations.

[00044] In certain embodiments, the inorganic particulate material is talc, such as macrocrystalline talc or microcrystalline talc or a combination thereof. The individual size of the platelets, that is, the average diameter, as measured by the Sedigraph method, of an individual talc platelet (a few thousand elementary leaves), can vary from approximately 1 µm to over 100 µm, depending on the conditions of deposit formation. The individual size of the platelets determines the ability to be lamellar from the talc. A highly lamellar talc will have large individual platelets, while a microcrystalline talc will have small platelets. Although all talc can be called lamellar, their platelet size differs from one deposit to another. The small crystals provide a compact and dense ore, known as microcrystalline talc. The large crystals come in layers of paper, known as macrocrystalline talc. The known microcrystalline talc deposits are located in Montana (Yellowstone) and Australia (Three Springs). In a microcrystalline structure, elemental talc particles are made up of small plates compared to macrocrystalline structures, which are made up of larger plates.

[00045] “According to certain modalities, the inorganic particulate material is a microcrystalline talc having a deao of about 50 µm or less, such as, for example, 30 µm or less, such as, for example, 20 µm or less , such as, for example, 10 µm or less, such as, for example, about 5 µm, and a dso of about 20 µm or less, such as, for example, 10 µm or less, such as, for example -, 5 µm or less, such as, for example, 3 µm or less, such as, for example, about 3 µm or about 1 µm.

[00046] According to certain modalities, the inorganic particulate material is bentonite, for example, a bentonite having one of about 100 µm or less, such as, for example, 80 µm or less, such as, for example, 70 µm or less, such as, for example, 65 µm or less, such as, for example, about 62 µm, and a dso of about 30 µm or less, such as, for example, 20 µm or less, such such as, for example, 19 μm or less, such as, for example, 18 μm or less, such as, for example, about 17 μm (all measured by wet Malvern laser scanning - ISO 13329- 1).

[00047] - As discussed above, the amounts of surfactant and inorganic particulate material need to be balanced, in order to prevent the inorganic particulate material from being moved into the aqueous phase by the surfactant, away from the water-air interface of the air bubbles. - puma, preventing it from developing its foam stabilizing properties.

[00048] According to certain modalities, the ratio of particulate inorganic powder to water in the aqueous composition according to the present invention can be in the range of 0.1 to 60% by weight, as, for example, in the range of 0.5% by weight to 60% by weight, such as in the range of 1% by weight to 60% by weight, for example in the range of 2% by weight to 50% by weight or in the range of 3% by weight to 20% by weight or in the range of 4 to 10% by weight, such as, for example, about 4% by weight or about 5% by weight or about

6% by weight or about 8% by weight or about 10% by weight or about 12% by weight. For example, according to the present invention, a composition ready to be foamed may have a ratio of particulate inorganic powder to water from about 1% by weight to about 6% by weight or about 3% in weight. A concentrate that requires dilution prior to foaming may have a surfactant to water ratio of about 10% by weight to about 60% by weight or about 30% by weight.

[00049] According to certain modalities, the ratio of particulate inorganic powder to surfactant in the aqueous composition according to the present invention can be in the range of 500: 1 to 1: 1, such as, for example, in the range of 300: 1 to 2: 1, or 250: 1 to 5: 1, or 200: 1 to 10: 1, or 100: 1 to 50: 1, such as, for example, about 200: 1, or about 100: 1, or about 50: 1. Other components and additives

[00050] Polymers that increase viscosity are known to the person skilled in the art and may include gums, such as xanthan gums. These can also act as film makers and foam stabilizers.

[00051] Mineral-based anti-sedimentation agents are known to the person skilled in the art. For example, atapulgite ("Atelgel 40", BASF), kaolin and / or sepiolite can be used.

[00052] Glycol ethers can be used as antifreeze agents, foam intensifiers and solvents.

[00053] Other additives that can be included in the compositions according to the present invention include corrosion inhibitors, antimicrobial additives, hardness ion scavengers, pH buffers and / or salts to control the formation of foam with soft water in order to allow the use of the compositions according to the present invention with fresh water or sea water,

as needed.

[00054] According to one embodiment, the aqueous composition according to the present invention comprises very few fluorinated compounds, such as, for example, less than 1% by weight of fluorinated compounds, or less than 1.0% by weight of fluorinated compounds, or less than 0.5% by weight of fluorinated compounds, or less than 0.1% by weight of fluorinated compounds, or less than 0.05% by weight of fluorinated compounds or less than 0 , 01% by weight of fluorinated compounds, or less than 0.001% by weight of fluorinated compounds or no detectable fluorinated compound. Dry precursor compositions

[00055] “Dry precursor compositions for preparing the aqueous compositions according to the present invention are also part of the present invention. According to one modality, the dry precursor composition consists of a particulate inorganic material, selected from the group consisting of perlite, talc, calcium carbonate, dolomite and bentonite and their combinations, and a surfactant and / or hydrotrope. Said particulate inorganic material and said surfactant and / or hydrotrope are combined in such quantities that, by mere addition of water, an aqueous composition according to the present invention can be obtained.

[00056] For example, the surfactant may comprise or consist of one or more anionic surfactants, or one or more cationic surfactants, or one or more nonionic surfactants, or combinations thereof, as discussed above in the case of aqueous compositions according to the present invention. In addition, for example, the particulate inorganic material can be selected from the materials, particle size and quality distributions, as discussed above in the case of aqueous compositions according to the present invention.

[00057] According to an embodiment of the present invention, the dry precursor composition further comprises one or more additives. Method of forming aqueous compositions

[00058] “In accordance with an embodiment of the present invention, aqueous compositions can be obtained by providing a dry precursor composition according to the invention and adding the necessary amount of water to obtain an aqueous composition according to the invention. According to another embodiment of the present invention, aqueous compositions can be obtained by mixing water and surfactant and / or hydrotrope in the necessary quantities and adding the particulate mineral material, under agitation, to obtain an aqueous composition according to invention. According to this modality, said particulate mineral material can be added in a dry state, or in a wet (aqueous) state, or as a suspension, such as, for example, an aqueous suspension.

[00059] The aqueous compositions according to the present invention can be transformed into foams in order to form a fire extinguishing foam, which is also part of the present invention. Use of aqueous compositions

[00060] - As discussed above, aqueous compositions can be used to form fire-extinguishing foams. As such, the compositions can be present in various concentrations, depending on whether they are intended to be foams as they are, or whether they can be diluted using a readily available water source. For example, in the case of compositions for use to extinguish fires at sea, such as for fires in oil and gas equipment and platforms, or in marine vessels, concentrated compositions that can be diluted with sea water before foam transformation can be stored. On the other hand, in places where water for dilution is not readily available, or where compositions need to be quickly foamed, such as in industrial facilities or at airports, the compositions can be kept in a concentration lower or ready-to-use aqueous dilution. Therefore, the aqueous compositions according to the present invention can be provided as concentrates with a low water content or as dilute aqueous compositions with a high water content. Therefore, the content of particulate inorganic powder in the aqueous compositions can be in the range of 0.1% by weight to 60% by weight, based on the total weight of the composition.

[00061] Aqueous compositions can be foamed using methods known to the person skilled in the art, that is, foamed by mechanical means. Such mechanical means may include foam nozzles or foam generators. The use of inorganic particulate materials, as discussed in this document, for the formation of fire extinguishing foams is part of the present invention. According to the present invention, the use of inorganic particulate materials leads to more stable foams that, in use, remain on the surface of a burning fuel in a class B fire with a low rate of decomposition. and a low mixing rate in the burning fuel.

[00062] Furthermore, even after decomposition or evaporation of the foam, the inorganic particulate materials present in the fire extinguishing composition remain in the system, because they are, in general, stable at the temperatures found in a class B fire. , without the expected decomposition below 1000ºC. Consequently, inorganic particulate materials can provide an insulating mat that will also retain its foam structure, even if the water in the foam has evaporated.

[00063] Finally, inorganic particulate materials for use in accordance with the present invention are readily available on the world market and do not present a risk of environmental pollution after use in a fire-fighting foam. The foams according to the present invention do not contain any fluorinated components and have a lower surfactant content than foams in the prior art. Foam expansion ratio (FER)

[00064] It was further found that the compositions according to the present invention had satisfactory to excellent foaming properties. Foam expansion ratios (FER) of close to 5 or more can be obtained with standard tap water, and even 8 to more than 20. As used in this document, FER was calculated by dividing the volume of the expanded foam by the volume of the solution before transformation into foam: FER = Vespuma / Vsolution:

[00065] It should be noted that the present invention may comprise any combination of the features and / or limitations referred to in this document, except for combinations of such features that are mutually exclusive. The foregoing description is directed to particular embodiments of the present invention for the purpose of illustrating it. It will be evident, however, for one skilled in the art, that many modifications and variations of the modalities described in this document are possible. All such modifications and variations are intended to be within the scope of the present invention, as defined in the appended claims.

EXAMPLES Examples 1a 5

[00066] Several particulate inorganic materials have been tested for their foam stabilizing properties.

[00067] Various inorganic particulate materials (10% by weight)

were mixed in a 0.3% by weight foam solution of sodium lauryl ether sulfate (MEYCO SLF 30, supplied by BASF) in water and the resulting compositions mixed using a laboratory foam generator. The resulting foams (60 g) were inserted into a funnel cell with a sufficiently thick frit, in such a way that the mineral particles did not block the water drainage of the foam, thus affecting the results, and a collector at the bottom and left in rest. Any foam decomposition was measured by measuring the amount of water collected under the funnel cell.

[00068] The tested particulate inorganic materials are shown in Table |: Table |: Pes

[00069] The amount of water collected was observed for 30 minutes. The results are shown in Table | l. The values shown are the values of the percentage of foam that remains inside the funnel cell and can be seen as a measure of foam stability over time. Table | l: [Timeout jo | 1 | 2 | 3 4 | 5 | 7s [10 [15 130 | [e es es Ta Te Te Ta 17 de 1a | ez ea fe ea te Te de | [es es Te Tr Tas 15 fas 5 17 115 | [sr and 7 [ro [76 [os [os [os [os des Tas | [Es re re [ro [Tee es lie fer 17 er |

[00070] It has been found that all inorganic particulate materials lead to improved foam stability. For Example 4 (talc), the stability after 60 minutes was 91%. The talc used in Example 4 is a microcrystalline talc having a dso of 5 µm and a dso of 1 µm. The talc used in Example 5 is a macrocrystalline talc having a diameter of 6.2 µm and a dso of 1.8 µm (by Sedigraph - ISO 13317-3). Examples 6 and 7

[00071] In another series of tests, a foam solution of 3% by weight of sodium lauryl ether sulfate (MEYCO SLF 30, supplied by BASF), in water and without inorganic particulate matter, was compared to other surfactants with and without inorganic particulate matter. Polymer A is sodium lauryl sulfate (SLS) and Polymer B is tetradecyltrimethylammonium bromide (TTAB). The compositions as shown in Table III were mixed using a laboratory foam generator. The talc used in Examples 6 and 7 is a macrocrystalline talc having one of 6.2 µm and a dso of 1.8 µm (by Sedigraph - ISO 13317-3). Table Ill:

[00072] The resulting foams (60 g) were placed in a funnel cell with a frit and collector at the bottom and left to rest. Again, any decomposition of the foam was measured by measuring the amount of water collected under the funnel cell. The results are shown in Table IV.

Table | V: [Time immin jo ds jo das ro as iso [scoomez Tm fer Tas dar Ta a e [accemp a 100 Jos Tas sr 129 Tas de

[00073] It is shown that the addition of 5% by weight of talc with the strong simultaneous reduction of surfactant from 3% by weight to 0.05% by weight leads to reduced foam decomposition for the SLS. In addition, it has been shown that the performance of TTAB is better than that of SLS. Examples 8 and 9

[00074] The foams were tested in the presence of various amounts of talc and tetradecyltrimethylammonium bromide (TTAB), using demineralized water (Example 8) or standard tap water (Example 9). The talc used was a microcrystalline talc supplied by Imerys Talc having a BET surface area of 21 m? / G (ISO 9277) and an average particle size of 1.1 µm (by Sedigraph - ISO 13317-3). TTAB was used as a 5% aqueous stock solution. The foams were prepared by combining the talc and the TTAB stock solution and making up to 100 g using demineralized or tap water. The resulting compositions were mixed using a laboratory foam generator. The resulting foams were placed in a funnel cell with a frit and collector at the bottom and left to rest. Any decomposition of the foam was measured by measuring the amount of water collected under the funnel cell. The varied test parameters are shown in Table V.

Table V:

[00075] The amount of water collected was observed for 30 minutes. The results are shown in Table VI. The values shown are the values of the percentage of foam that remains inside the funnel cell and can be seen as a measure of foam stability over time. The values shown in the "FER" column indicate the foam expansion ratios obtained.

Table VI: [emso me To Ts Tio Tas Tao Tas Tao TrER [echo - [ro 17 17 Jor fes es Tor es [eco - ro sr 176 175 170 es des 17 [eee - 100 [oo 176 Jos Tea Tso 156 169 [ gs 100 fans [oo 155 Ta Tas [or 1225 er 1 [16 fans 5 sr 175 and ss are Ts Tm 15 Ta 25 Tm mer | [sm - o 7 7 and Te e 5a and Fm Tm of 5 Ta Ta 175 ses 5 5 and 1 7 and res

EXE LELELELEVECOS

[00076] All Examples have been found to lead to improved foam stability over Ex. Comp. 1 (see Table 11 above). Examples 10 to 17

[00077] Foams have been tested in the presence of various amounts of talc and surfactants, using standard tap water. The talc used in Examples 10 to 12 was a microcrystalline talc supplied by Imerys Talc having a BET surface area of 21 m? / G (ISO 9277) and an average particle size of 1.1 µm (by Sedigraph - ISO 13317-3 ). The talc used in Examples 13 to 15 was a microcrystalline talc having an average particle size of 0.5 µm (by Sedigraph - ISO 13317-3). The talc used in Examples 16 and 17 was synthetic talc, as explained below. The foams were prepared by diluting stock solutions to 3% by weight of various surfactants in water, to obtain diluted solutions of surfactant in water, followed by the addition of talc and making up to 100 g with tap water. The resulting compositions were mixed using a laboratory foam generator. The resulting foams were placed in a funnel cell with a thick frit and collector at the bottom, and left to rest. Any foam decomposition was measured by measuring the amount of water collected under the funnel cell. The varied test parameters are shown in Table VII.

[00078] Said synthetic talc was obtained according to methods that include the solvothermal treatment at a pressure greater than 1

MPa and at temperatures from 100ºC to 600ºC, as disclosed in WO 2015/159006 (continuous process) or WO 2008/009799 (batch process). The synthetic talc obtained in this way was characterized by X-ray diffraction analysis, in which the diffraction pattern showed a peak located at a distance of the order of 9.40 to 9.68 À, for a plane (001), a peak located at 4.50 to 4.75 À, for a plane (020), a peak located at 3.10 to 3.20 À, for a plane (003), and a peak located at 1.50 to 1 , 55 À, for a plane (060). The synthetic talc has an average particle size dso of 500 nm and a BET surface area in the range of 300 to 500 m? / G. Table VII:

[00079] —Sodium lauryl sulfate (SLS) and sodium lauryl ether sulfate (SLES) have been compared to the Arquad C-35. ARQUAD C35 is a 35% by weight solution of cocotrimethylammonium chloride in water. The amount of water collected was observed for 30 minutes. The results are shown in Table VIII. The values shown are the values of the percentage of foam that remains inside the funnel cell and can be seen as a measure of foam stability over time. The values shown in the "FER" column indicate the foam expansion ratios obtained.

Table VII: reset to 5 1 1 sm) mo a to 7 1) at e | [and | | os) EE ms to Ss 6) E q ms to ss) sm but ss 7) [sm o o | o [558 [ss | the [in 0 | 100 | 100 | 109 | 699 | 102

[00080] All Examples have been found to lead to improved foam stability over Ex. Comp. 1 (see Table 11 above). Examples 18 to 23

[00081] The foams were tested in the presence of various amounts of talc, which had been moistened with a 15% solution by weight of surfactant in water, using standard tap water. The talc used in Examples 18 to 23 was a microcrystalline talc supplied by Imerys Talc, having a BET surface area of 21 m2 / g (ISO 9277) and an average particle size of 1.1 µm (by Sedigraph - ISO 13317 -3), which had been constituted as a wet talc composition comprising talc and 15% by weight of surfactant in water. The water was added gradually, while mixing, to obtain the aqueous solution, which was subsequently foamed. Foam stability was tested in the same way as for Examples 10 to 17 (see above). The compositions used and the results are shown in Tables IX and X.

Table IX:

[00082] In Examples 18 to 20, the compositions were made into foams immediately after formation. In Examples 21 to 23, the compositions were foams 7 days after formation.

Table X: [Tempoímin - Jo Ts Tm Tw5 so FER | [there is oo 100 oo 82 and 7a | [ext oo 100 Too dos ar 1157 | [ez “oo dos oo sr j8s 65 | [ex 100 f100 oo es es 206 | [8x2 oo 100 joe os 86 157 | [xa jo das jar sr js so | Examples 24 and 25

[00083] The foams were tested in the presence of various amounts of talc, which had not been moistened before use and before being mixed with the surfactants, using standard tap water. The talc used in Examples 24 to 25 was a microcrystalline talc supplied by Imerys Talc, having a BET surface area of 21 m? / G (ISO 9277) and an average particle size of 1.1 µm (by Sedigraph - ISO 13317-3), which had been mixed with the SLS in a 100: 1 weight ratio (5 g of talc and 0.05 g of SLS), before adding water. The water was added to obtain 100 g of aqueous composition, which was subsequently foamed, giving aqueous foams comprising 0.05% by weight of SLS and 5% by weight of talc. Foam stability was tested in the same way as for Examples 10 to 17 (see above). In Example 24, the composition was foamed immediately after formation. In Example 25, the composition was foamed 14 days after formation. The results are shown in Table Xl. Table XI: Temple - [15 Tm to Tr ea area [109 1109 [100 Tas Tas | [8 ro 16 ros Te Too 12 | Examples 26 to 55

[00084] The foams were tested in the presence of equal amounts of various microcrystalline and macrocrystalline talc and tetradecyltrimethylammonium bromide (TTAB), using standard tap water. The foams were prepared and tested in the same way as in the previous examples. The results are shown in Table XII. Average dso particle sizes, as measured by Sedigraph (ISO 13317-3), are indicated. Foam stability is indicated by the time required to drain 30% of the water from the foam.

Table XII: Ex. Of time Ex. Of time Ex. Of time (one) (min) (one) (min) (one) (min)

[00085] The results are represented graphically in Fig. 1,

which also represents the geographical origin of the different talc. Although the graph indicates that there is some influence on the stability of the foam from the origin of the talc, the biggest effect is the particle size; the finer the talc, the more stable the foam. Example 56

[00086] Foams were tested in the presence of 1.0% by weight or 0.5% by weight of different minerals and sodium laurel sulfate (SLS). The talc used was a high apparent ratio (HAR) talc provided by Imerys Talc, having a BET surface area of 19 m? / G (ISO 9277) and an average particle size of 2.1 µm (by Sedigraph - ISO 13317-3). The calcium carbonate used was a precipitated calcium carbonate (PCC) supplied by Imerys, having a BET surface area of 19 m? / G (ISO 9277) and an average particle size of 2.1 µm (by Sedigraph - ISO 13317 -3). The bentonite used was a bentonite supplied by Imerys, having a BET surface area of 54.4 m2 / g (ISO 9277) and an average particle size of 16.8 µm (by Malvern laser spreading to wet - ISO 13329-1). The mica used was a mica supplied by Imerys, having 64% of particles having a particle size below 2 µm (measured by Sedigraph - ISO 13317-3). SLS was used as a 3% aqueous stock solution. The foams were prepared by combining the mineral and the SLS stock solution and making up to 100 g using water. The resulting compositions were mixed using a laboratory foam generator. The resulting foams were placed in a funnel cell with a frit and collector at the bottom and left to rest. Any foam decomposition was measured by measuring the amount of water collected under the funnel cell. The varied test parameters are shown in Table XIII.

Table XIII:

[00087] The amount of water collected was observed for 30 minutes. The results are shown in Table XIV. The values shown are the values of the percentage of foam that remains inside the funnel cell and can be seen as a measure of the foam's stability over time. The values shown in the "FER" column indicate the foam expansion ratios obtained.

Table XIV: Tempoími - o Ts To Ts To rx [this is T77s Jess [452 [254 [this 100 eos Tones [497 562 [244 |

[00088] Examples 56b to 56d and Example 56i have been found to lead to improved foam stability over Comparative Example 56a (see Table XIV above). Examples 56e to 56h and Examples 56j and 56k have an equivalent or deteriorated foam stability, but which remains acceptable.

However, it was also unexpected that all of the above minerals have surprisingly been shown to reduce or eliminate the transmission of flammable vapors through the foam, compared to Comparative Example 56a.

Claims (19)

1. Aqueous composition for fire suppression, characterized by the fact that it comprises a surfactant and / or a hydrotrope; a particulate inorganic material, selected from the group consisting of perlite, talc, calcium carbonate, kaolin, dolomite, mica and bentonite, and their combinations, and optionally, one or more additives. 2. Aqueous composition, according to claim 1, characterized by the fact that said surfactant is selected from the group of cationic surfactants, non-ionic surfactants and anionic surfactants. 3. Aqueous composition according to claim 2, characterized by the fact that the surfactant is a cationic surfactant, such as, for example, an alkyl trimethyl ammonium halide, such as tetradecyl trimethyl ammonium bromide or dicocodimethylammonium chloride , or dihydrogenated tallow-oilethyl hydroxyethylammonium methosulfate, or a polymeric quaternary ammonium ester. 4. Aqueous composition according to claim 2, characterized by the fact that the surfactant is an anionic surfactant selected from alkyl ether sulfates, such as sodium lauryl ether sulfate, and alkyl sulfates, such as sodium lauryl sulfate. 5. Aqueous composition according to any one of the preceding claims, characterized by the fact that the inorganic particulate material is selected from the group consisting of talc, calcium carbonate, mica and kaolin. 6. Aqueous composition according to claim 5, characterized by the fact that the inorganic particulate material is talc, such as, for example, microcrystalline talc, macrocrystalline talc or a mixture of them. 7. Aqueous composition according to claim 5 or 6, characterized by the fact that the inorganic particulate material is synthetic talc. Aqueous composition according to claim 5 or 6, characterized by the fact that said talc is a microcrystalline talc having a dso of 10 µm or less, like 5 µm or less, ranging from 0.01 to 3.0 µm, such as about 0.01 µm, or about 1.0 µm, or about 2.0 µm. 9. Aqueous composition according to any of the preceding claims, characterized by the fact that the ratio of surfactant to water is in the range of 0.01 to 5% by weight. Aqueous composition according to any one of the preceding claims, characterized by the fact that the content of particulate inorganic powder in the composition is 0.1 to 60% by weight, based on the total weight of the composition. 11. Aqueous composition according to any one of the preceding claims, characterized by the fact that the weight ratio of particulate inorganic powder to surfactant is in the range of 500: 1 to 1: 1. Dry precursor to the aqueous composition, as defined in any one of claims 1 to 11, characterized by the fact that it comprises a surfactant and / or a hydrotrope, and a particulate inorganic material, selected from the group consisting of perlite, talc , calcium carbonate, dolomite, mica and bentonite and their combinations and, optionally, one or more additives. 13. Dry precursor, according to claim 12, characterized by the fact that the weight ratio of particulate inorganic powder to surfactant is in the range of 500: 1 to 1: 1. 14. Fire extinguishing foam, characterized by the fact that it comprises an aqueous composition or a similar precursor as defined in any of the preceding claims. 15. Method of preparing a fire extinguishing foam, as defined in claim 14, characterized by the fact that it comprises the steps of providing a mixture of water and surfactant and / or a hydrotrope; provide a particulate inorganic material, selected from the group consisting of perlite, talc, calcium carbonate, dolomite, mica and bentonite and their combinations; optionally providing one or more additives; mixing said mixture of water and surfactant and / or a hydrotrope, said particulate inorganic material and, optionally, said one or more additives; transform the obtained mixture into foam. 16. Method of preparing a fire extinguishing foam, as defined in claim 14, characterized by the fact that it comprises the steps of providing a dry precursor, as defined in claim 12 or 13; provide water; optionally providing one or more additives; mixing said dry precursor, said water and, optionally, said one or more additives; transform the obtained mixture into foam. 17. Use of a particulate inorganic mineral, as defined in any of the preceding claims, or an aqueous composition, as defined in any of claims 1 to 11, or the dry precursor, as defined in claim 12 or 13, characterized by the fact that it is in the preparation of a fire extinguishing foam. 18. Use, according to claim 17, characterized by the fact that said particulate inorganic mineral is selected from the group consisting of perlite, talc, calcium carbonate, dolomite, mica and bentonite, and their combinations. 19. Fire extinguishing method, for example, a class B fire, characterized by the fact that it comprises the use of a particulate inorganic mineral, as defined in any of the preceding claims, or an aqueous composition, as defined in any one of claims 1 to 11, or the dry precursor, as defined in claim 12 or 13, or the fire extinguishing foam, as defined in claim 14.